Monoazo pigments and textiles decorated therewith



United States Patent Claims. (Cl. 117-121 ABSTRACT OF THE DISCLOSURE Textile fabrics decorated with resin-bonded pigments, wherein the pigments are monoazo pigments made by coupling diazotized 3-amino-4-methyl -benzamide with certain Naphthol AS type coupling components.

This application is a divisional application of application Ser. No. 389,774 filed Aug. 14, 1964, now Patent No. 3,332,932, which is a continuation-in-part of application Ser. No. 165,929 filed Jan. 12, 1962.

This invention relates to monoazo pigments and textiles decorated therewith. More particularly, the invention relates to certain pigments made by coupling diazotized 3-amino-4-methyl benzamide With certain Naphthol AS type coupling components, especially Naphthol AS [l-(2',3-hydroxy-naphthoylamino) benzene], Naphthol AS-RT [1-(2',3'-hydroxynaphthoylamino)-4-methyl benzene], Naphthol AS-RL [1-(2',3'-hydroxynaphthoylamino)-4-rnethoxy benzene], Naphthol AS-PH [1-(2',3'- hydroxynaphthoylamino)-2-ethoxy benzene], Naphthol AS-E [1 (2',3' hydroxynaphthoyl-amino)-4-chlorobenzene], Naphthol AS-MX [1-(2',3-hydroxynaphthoylamino)-2,4-dimethyl benzene], Naphthol AS-KB [1-(2', 3' hydroxynaphthoylamino)-2 methyl-4-chlorobenzene], Naphthol AS-ITR [1-(2,3'-hydroxynaphthoytlamino)-2,4- dimethoxy-S-chlorobenzene], and Naphthol AS-SW [2- (2'3'-hydroxynaphthoylamino -na-phthalene] The art of coloring textiles with pigments is well advanced but there is a continuing search for pigments having improved properties. In recent years the desire for a bright red or scarlet pigment having good dry cleaning and other properties, such as resistance to discharge agents, has increased, for instance, to print or color dress goods. At the time we started our researches to find an improved red pigment having good dry cleaning resistance one of the best red pigments for brightness and dry clean resistance was the monoazo pigment described in US. Patent 2,915,518 as being made by diazotizing 3- amino-4-methoxy benzanilide and coupling to l-(2',3-

,hydroxynaphtholyamino) 2,5 dimethoxy-4-chlorobenzene.

In our search for red pigments having improved properties for decorating textiles we have prepared numerous pigments by coupling BO'N (B-oxynaphthoic acid) type naphthols with diazotized 3-aminobenzamide and its substitution derivatives.- We have found that nine of these pigments, i.e., those enumerated above, have very desirable and unexpectedly good properties for pigment dyeing or pigment printing of textiles. Those pigments made by coupling diazotized 3-amino-4-methyl 'benzamide with Naphthol AS, Naphthol AS-RT, Naphthol AS-RL, Naphthol AS-PH, Naphthol AS-E, Naphthol AS-MX, Naphthol AS-KB, Naphthol AS-ITR and Naphthol AS- 3,399,077 Patented Aug. 27, 1968 SW, when printed or pad-dyed on textile fabrics give very bright red and scarlet decorations that have unexpectedly good fastness to drycleaning while still possessing satisfactory lightfastness, washfastness, and discharge resistance. Such decorated textile fabrics constitute a preferred embodiment of our invention.

Some of the desirable pigments referred to hereinabove are novel, namely, those made by coupling diazotized 3- amino-4-methyl benzamide with Naphthol AS-RT, Naphthol AS-RL, Naphthol ASPH, Naphthol AS-E, Naphthol AS-MX, Naphthol ASITR, and Naphthol AS-SW, and these new pigments constitute another preferred embodiment of our invention.

Although the above pigments made by coupling diazotized 3-amino-4-methyl benzamide with Naphthol AS is mentioned in the prior art as a pigment for rubber that is subsequently vulcanized, there is no teaching or suggestion of its use to make the decorated textiles claimed in the present invention. Further, other prior art mentions pigments that have seemingly similar chemical structures to the presently claimed pigment but these seemingly similar pigments do not suggest or make it possible to predict the desirable properties of the pigments claimed in the present application. Our new pigments, when applied to textiles, appear to exhibit much better drycleaning resistance and discharge resistance than do the prior art pigments of closest similarity.

The following examples in which the parts are by weight will further illustrate the invention.

EXAMPLE 1 150 parts of 3-amino-4-methy-l benzamide, suspended in 1500 parts of water is diazotized in the usual manner with 265 parts of concentrated hydrochloric acid and 72 parts of sodium nitrite. To the cold diazo buffered with 161 parts of acetic acid and 65 parts of sodium acetate there is added with good stirring the solution made from 298 parts of 1-(2'3-hydroxynaphthoylamino)-4-chlorobenzene (Naphthol AS-E), 1500 parts of hot water and 127 parts of caustic soda. After stirring for some time the pigment slurry is heated between C. and 95 C. and filtered. An exceptionally bright scarlet pigment is obtained having good drycleaning and discharge resistance, and good light fastness when pad-dyed or printed on textiles.

The above pigment can be easily incorporated into conventional textile decorating vehicles such as those described in US. .Patents 2,222,581; 2,222,582; 2,267,620; 2,364,692; 2,533,270; 2,539,914; 2,540,048; 2,600,890; 2,691,005; 2,865,871 and 2,897,165. When the pigment is to be incorporated into a water-immiscible vehicle it is easily flushed from the aqueous pulp or press-cake into the desired vehicle by conventional pigment flushing technique. This technique can be used to produce commercial color concentrate dispersions, containing a minimum of water, and containing as essential components, pigments, thermosetting resin, dispersing agent and volatile solvents.

When the above pigment is incorporated into water-inoil emulsion print pastes or oil-in-water emulsion print pastes and printed on cotton cloth it gives scarlet prints of excellent brightness, very good drycleaning resistance (AATCC color fastness to Dry Clean Test Method 1960), good lightfastness and good discharge resistance. Good discharge resistance means that the pigment is substantially unaffected by reducing agents used in discharge printing on previously dyed fabrics. Such discharge printing techniques are described in some of the above cited patents and in No. 2,267,620 in particular.

w 3 XAMPLE 2 In a manner similar to Example 1, the diazonium salt of 3-amino-4-methyl benzamide was coupled with 1-(23- hydroxy-naphthoylamino) 4-methoxybenzene to give a scarlet pigment having the formula CONH:

NEEQ In a manner similar to Example 1, the diazonium salt of 3-amino-4-methyl benzamide was coupled with 1-(2,3'- hydroxy-naphthoylamino) 4-methyl benzene to give a scarlet pigment having the formula CONHl l -on on.

The pigment can be easily incorporated into conventional textile decorating vehicles to give bright red, or scarlet, prints and dyeings on textiles having good drycleaning resistance, light fastness and discharge resistance. Like the pigment of Example 1, the above pigment is easily flushed from the aqueous pulp into water-immiscible vehicles. Prints on cotton cloth were very bright, had good fastness to drycleaning and to light, and had good discharge resistance.

EXAMPLE 4 In a manner similar to Example 1, the diazonium salt of 3-amino-4-methyl benzamide was coupled with 1-(2',3'- hydroxy-naphthoylamino)benzene to give a red pigment having the formula The pigment can be easily incorporated into conventional textile decorating vehicles to give bright red, or scarlet,

- prints and dyeings having good drycleaning resistance,

lightfastness and discharge resistance. Like the pigment of Example 1, the above pigment is easily flushed from the aqueous pulp into water-immiscible vehicles; Prints on cotton cloth were very bright, and good fastness to drycleaning and to light, and had good discharge resistance.

EXAMPLE 5 In a manner similar to Example 1, the diazonium salt of 3-amino-4-methyl benzamide was coupled with 1-(2,3- hydroxy-naphthoyl-amino)-2-ethoxy benzene to give a scarlet pigment having the formula The pigment can be easily'incorporated into'conventional textile decorating vehicles to give bright red, or scarlet, prints and dyeing having good dry cleaning resistance, light fastness and discharge resistance. Like the pigment of Example 1, the abovepigment is easily flushed from the aqueous pulp into watenimmiscible vehicles. Prints on cotton cloth were very bright, had good fastness to drycleaning and to light, and had good discharge resistance.

EXAMPLE 6 In a manner similar to Example 1, the diazonium salt of 3-amino-4-methyl benzamide was coupled with l-(2',3' hydroxy-naphthoylarnino)-2,4-dimethyl benzene to give red pigment having the formula CONH;

. O-NHQ-CH:

The pigment can be easily incorporated into conventional textile decorating vehicles to give bright red prints and dyeings on textiles having good drycleaning resistance, light fastness and discharge resistance. Like the pigment of Example 1, the above pigment is easily flushed from the aqueous pulp into water-immiscible vehicles. Prints on cotton cloth were very bright, and good fastness to drycleaning and to light, and had good discharge resistance.

EXAMPLE 7 In a manner similar to Example 1, the diazonium salt of 3-amino-4-methyl benzamide was coupled with 1-(2',3'- hydroxy-naphthoylamino) Z-methyl-chloro benzene to give a red pigment having the formula CONH:

l A on on, 01 K c ONH The pigment can be easily incorporated into conventional textile decorating vehicles to give bright red prints and dyeings having good drycleaning resistance, light tastness and discharge resistance. Like the pigment of Example 1, the above pigment is easily flushed from the aqueous pulp into water-immiscible vehicles. Prints on cotton cloth were very bright, had good fastness to drycleaning and to light, and-had good discharge resistance.

EXAMPLE 8 In a manner similar to Example 1, the diazonium salt of 3-amino-4-methyl benzamide was coupled with 1-(2',3'- hydroxy-naphthoylamino) 2,4-dimethoxy-5-chloro benzene to give a red pigment having the formula The pigment can be easily incorporated into conventional textile decorating vehicles to give bright red prints and dyeings having good drycleaning resistance, light fastness and discharge resistance. Like the pigment of Example 1, the above pigment is easily flushed from the aqueous pulp into water-immiscible vehicles. Prints on cotton cloth were very bright, and good fastness to drycleaning and to light, and had good discharge resistance. r

EXAMPLE 9 I In a manner similar to Example 1, the diazonium salt of 3-amino-4-methyl benzamide was coupled with 1-(2,3'- hydroxy-naphthoylamino) 2-naphthalene to give a red pigment having the formula ONE:

t? @(lza The pigment can be easily incorporated into conventional textile decorating vehicles to give bright red prints and dyeings having good drycleaning resistance, light fastness and discharge resistance. Like the pigment of Example 1, the above pigment is easily flushed from the aqueous pulp into water-immiscible vehicles. Prints on cotton cloth were very bright, had good fastness to drycleaning and to light, and had good discharge resistance.

A typical water-in-oil emulsion textile decorating composition for printing on textiles would be as follows:

Parts by weight Butadiene-acrylonitrile copolymer elastomer latex,

40% solids 10.00

Prints on cotton using this print paste were very bright red, had excellent drycleaning resistance when subjected to the standard AATCC Test 85-1960, only slight fading after 20 hours exposure in the Fadeometer and only a trace or no color loss when subjected to a No. 3A washfastness test. Some very similar pigments, for example the pigments made by coupling the diazonium salt with Naphthol AS-RP [1 (2,3-hydroxynaphthoyl-amino)-4- ethoxy benzene] and Naphthol AS-TIR [l-(2,3'-hydroxynaphthoylamino)-2-methyl-4-chlorobenzene], when substituted in the above formulation and printed on cotton, showed a definite though moderate color loss in the drycleaning test and considerable color loss in the washfastness test. Other similar pigments, e.g., those made according to Example 1, but using 3-amino-4-chloro benzamide instead of 3-amino-4-methyl benzamide, gave prints that showed a definite color loss in the dry-cleaning test;

the pigment made by coupling diazotized 3-amino-4-chloro benzamide to Naphthol AS-TR gave prints that lost most of their color when subjected to the drycleaning test.

An oil-in-water emulsion textile printing composition is illustrated by the following:

Parts by weight Pigment of Example 2 2.00 Sodium lauryl sulfate .40 Ammonium sulfate .21 Methyl cellulose, 15 centipoise grade .16 Methyl cellulose, 4000 centipoise grade .28 Ammonium polyacrylate .60 Ammonia water, 28% ammonia .20

'Butadiene-styrene copolymer elastomer latex, 40%

solids 2.40 Melamine-formaldehyde resin, 50% solution in 50/50 xylol-butanol 1.00 Water 52.25 Varsol No. 2 (petroleum hydrocarbon solvent,

kauri-butanol value 33-45 and boiling range 306-394 F.) 30.50 Butadiene-acrylonitrile copolymer el-astomer latex,

40% solids 10.00

This printing composition gave very bright red prints on cotton having exceptionally good drycleaning resistance in that it showed substantially no color loss when subjected to the standard AATCC Test Method -4960 and showed substantially no color loss when subjected to a No. 3A Wash Test. The prints showed substantially no fading after 30 hours exposure in the Fadeometer. Surprisingly, a very similar pigment chemically, i.e., the pigment made by coupling diazotized 3-amino-4-methyl benzamide to Naphthol AS-OL [l-(2'3'-hydroxynaphthoylamine)-2-methoxy benzene], showed definite color loss in the drycleaning test, withstood only 10 hours in the Fadeometer without substantial fading, and showed moderate to considerable color loss in the washfastness test. Another similar pigment chemically, i.e., the pigment from coupling the same diazonium compound to Naphthol AS-RP [1 (2,3 hydroxynaphthoylamino)-4-ethoxybenzene] was similar to the Naphthol AS-Ol coupling. Also, the pigment made by replacing the 3-amino-4- methyl benzamide of the Example 2 pigment with 3- amino-4-chlorobenzamide gave much inferior drycleaning resistant prints than the Example 2 pigment.

Each of the other pigments in Examples 3 to 9 give bright prints on cotton when substituted in either the above water-in-oil emulsion or oil-in-water emulsion printing formulations, give prints that show substantially no color loss in drycleaning test and in most cases substantially no color loss in the 3A Wash Test. Also, most of these pigments withstand at least 20 hours in the Fadeometer without fading.

The pigments can also be applied to textiles by the paddyeing process. A suitable formulation is as follows:

Parts by weight Pigment (Examples 1 to 9) .20 Non-ionic surfactant, e.g., Igepal CA (an ethylene While the invention has been described with particular reference to the decoration of cotton fabrics, it is to be 7 s understood that the invention is notilir ni ted 61112; ae 'ag titile fabrirfdeco'rated with ifpigiiieritas in claim tion of any particular fabric. The invention is applicable 1 where R is the 4-methoxypheny1' groi1p: to the decoration of textile fabrics in general. 3. A textile fabric decorated with a pigment as in claim We claim: 1 where R is the 4-methyl phenyl group. 1. A textile fabric decorated with a pigment of the 5 4. A textile fabric decorated with a pigment as in claim group consisting of azo pigments havingthe formula 1 W re R s t -C Q Y phenyl-group.

-. r 5. A textile fabric dec'orated with a pigment as in claim (IJONH, 1 where R is the 4-chloro phenyl group. I m a R r es te 0 a A *UNITEE seams 'PA'TE'NT'S" OH H:

2,006,211 6/1935 Fisher 260-203 X 2,899,421 8/1959 Fisher 260-204 15 FOREIGN PATENTS where R is a substituted aryl group selected from [phcn- 921,592 12/ 1954 yyl], 4-methyl phenyl, 4-methoxy phenyl, 2-ethoxy phenyl, 4-chloro phenyl, 2,4-dimethyl phenyl, 2-methyl-4-chloro WILLIAM MARTINPrmary Exammer' phenyl, 2,4-dimethyl-5chloro phenyl, and naphthyl. T. G. DAVIS, Assistant Examiner. 

